Free Thiols Regulate the Interactions and Self-Assembly of Thiol-Passivated Metal Nanoparticles

Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols). Simulations demonstrate that the presence of free thiols produces a nearly symmetrical coating of ligands on the core. X-ray measurements show that above a critical value of core-ligand coverage the nanoparticle core rises above the water surface, the edge-to-edge distance between neighboring nanoparticles increases, and the nanoparticle coverage of the surface decreases. These results demonstrate the important role of free thiols: they regulate the organization of bound thiols on the core and the interactions of nanoparticles with their surroundings.

Automated summary

Thiol ligands bound to nanoparticles determine their interactions and self-assembly, with the presence of free thiols affecting the coverage on the core. X-ray scattering and MD simulations show that free thiols result in a symmetrical coating of ligands on the core, while exceeding a critical value of core-ligand coverage leads to changes in nanoparticle positioning and coverage on the surface. This highlights the crucial role of free thiols in regulating the organization of bound thiols on the core and nanoparticle interactions with the surroundings.